Process for hydrogenating distillable carbonaceous materials



M. PIER ET AL July 20, 1937.

PROCESS OF HYDROGENATING DISTILLABLE CARBONAGEOUS MATERIALS original Filed Dec. 221, 1932 QOL. WNTDW.

Patented 'July 2o, 1937 UNITED STATES PROCESS FOR HYDROGENATING DISTILL- ABLE CARBONACEOUS MATERIALS Mathias Pier, Heidelberg,

and Walter s1- mon and Walter Kroenig, Ludwigshafen-onthe-Rhine, Germany, assignors to Standard- I. G. Company, Linden, N. J., a corporation of Delaware Original application December 22, 1932, Serial January 2, 1932 4 claims.

The present application has been divided out from our copending application Ser. No. 648,436 which relates to the hydrogenation of distlllable carbonaceous materials in the presence of iodine compounds of copper, titanium, tin and manganese.

In a further copending application Ser. No. 648,435 now Patent 2,028,348 led at the same date as the said application Ser. No. 648,436 we have claimed a process in which distillable carbonaceous materials are hydrogenated in the presence of a catalyst consisting of molybdenum bromide and tungsten sulfide.

It has already been proposed in the production of valuable hydrocarbon products, and in particular those of low boiling point, by destructive hydrogenation of distillable carbonaceous materials, by treatment with hydrogen or gases containing hydrogen at temperatures above 300 C. and under elevated pressure, to work in contact with catalysts containing halogens in a free or combined state.

We have now found that particularly good results are obtained in the treatment with hydrogenating gases of distillable carbonaceous materials, by working in contact with catalysts consisting of or containing (preferably to an extent of at least 10 per cent by weight) an iodine compound of nickel or cobalt or mixtures thereof.

More particularly the iodides of the said metals come into question.

It is not necessary for other catalysts to be simultaneously present, since the said iodine compoupds themselves have a very considerable catalytic activity.

, Improved results are however usually obtained by employing the said iodine compounds simultaneously with other compounds of metals of the second to the eighth group of the periodic system or mixtures of these, and more particularly the oxides, hydroxides or sulphides of the said metals. Especially good results are obtained with the compounds of metals of the groups 5 and 6 of the periodic system. The addition of other compounds of heavy metals as for example compounds of copper, silver, zinc, tin, cadmium,

manganese, uranium, rhenium and especially nickel or cobalt and more particularly the oxides, hydroxides, sulphides or carbonates of said heavy metals give very good results. Compounds such as oxides, hydroxides, sulphides or carbonates of lithium, magnesium or aluminium may also be employed. Elementary silicon or compounds thereof may also be present.

The nitrides, phosphides, borides, arsenides and Divided and this application ctober 18, 1934, Serial No. 748,884.

In Germany selenides of the metals of groups 2 to 8 of the periodic system also form suitable additions.

As examples of metals of the said groups 2 to 8 which may be used with advantage may be mentioned zinc, titanium, tin, lead, vanadium, manganese and silver. Y

Particularly good results are obtained by employing the said iodine compounds in conjunction with sulphides of metals of groups or 6 of the periodic system or of nickel or cobalt. In particular the sulphides of the metals molybdenum, tungsten, chromium, vanadium and uranium have proved useful.

When working with an addition of the said metal sulphides the aforesaid iodine compounds may be replaced by halogen compounds other than compounds of iodine as for example the compounds of bromine or chlorine of nickel or cobalt or mixtures thereof. In this case the halogen-compounds of chromium may also be employed.

Carrier substances or substances having a dispersing action, and which sometimes also have a catalytic action for example active carbon, silica gel, pumice stone or porous sherds of burned re clay may also be employed.

About 0.01 to 10 per cent by weight of said halogen compounds may be added to the initial materials. When treating coal pastes or hydrocarbons of high boiling point which are passed out of the reaction vessel together with the reaction products, preferably an amount of catalyst of between 0.01 and 5 per cent by weight is employed, whereas in the treatment of liquid hydrocarbon initial materials of high boiling point when the benzine and middle oil fractions distil oi from the reaction vessel whilst the higher boiling products remain therein, it may be .advantageous to work with a higher concentration of catalyst. l

As initial materials for treatment in accordance with the presentI invention may be employed coals of all varieties such as pit coal or brown coal, as such or made into a paste or suspension in oil, shale, peat, tars, mineral oils, shale oils or the distillation, conversion or extraction products from the same, as for example, products obtained by cracking or destructive hydrogenation. Good results are also obtained by the process accordingto the present invention in the destructive hydrogenation of asphalts or resins.

The catalysts in accordance with the present invention may be employed when working in the liquid, gaseous or solid phase.

The catalyst may be introduced into the reaction vessel at any suitable point. Thus it may be mixed withthe initial materials prior to their introduction into the preheating zone, where such is employed, or`only after preheating, or the catalyst may be introduced directly into the reaction vessel. If desired, and more particularly when working in the gaseous phase, the reaction vessel may be packed with catalyst or the catalyst may be arranged on suitable supports in the reaction vessel, which may if desired be movable. In this case it is not essential also to mix catalyst with the initial materials.

'Ihe catalyst may, if desired, be wholly or in part employed in a finely ground state, the grinding being even carried down to colloidal dimensions. Solid carbonaceous initial materials may be impregnated with a solution of the catalytic material.

'I'he expression treatment with hydrogenating gases of distillable carbonaceous materials is intended to comprise the most varied reactions, and the catalysts employed in accordance with the present invention have been found to be particularly advantageous in all of these said reactions. Thus the expression includes more particularly the destructive hydrogenation of carbonaceous materials, such as coal of all varieties, including lignite, other solid carbonaceous materials such as peat, shales and wood, or mineral oils, tars and the distillation, conversion and extraction products thereof, to produce hydrocarbons of all sorts, such as motor fuels and in particular anti-knock motorfuels, middle oils, kerosene and lubricating oils. The said expression also includes the removal of non-hydrocarbon impurities, such as sulphur or oxygen-containing substances or nitrogen compounds by the action of hydrogen or gases containing 0r supplying hydrogen from crude carbonaceous materials, for example the refining by treatment with hydrogen of crude benzol, of crude motor fuels or of lubricating oils. The said expression further includes the conversion of oxygen or sulphur containing organic compounds to produce the corresponding hydrocarbons or hydrogenated hydrocarbons, for example, the conversion of phenols or cresols into ,the corresponding cyclic hydrocarbons or hydrogenation products thereof. Finally it includes the hydrogenation of unsaturated compounds and more particularly of unsaturated hydrocarbons or of aromatic compounds and more particularly of aromatic hydrocarbons, for example, to produce hydroaromatic hydrocarbons.

'I'he said .reactions with hydrogen or hydrogen containing gases are usually carried out at temperatures between 250 and '700 C. and as a rule between 380 and 550 C. The pressures employed are usually in excess of 20 atmospheres and as a rule preferably in excess of 50 atmospheres. In some reactions, however, for example in the refining of crude benzol, rather low pressures, for example of the order of 40 atmospheres may be employed. Generally however pressures of about 100, 200, 300, 500 and in some cases even 1000 atmospheres come into question.

'Ihe amount of hydrogen maintained in the reaction space, and parts connected therewith, if any, varies greatly with the nature of the particular initial materials treated or according to the result in View. In general 400, 600, 1000 cubic meters or more of hydrogen measured under normal conditions of temperature and pres-Y sure, per ton of carbonaceous material treated may be used.

The gases for use in the reaction may consist of hydrogen alone or of mixtures containing hydrogen (for example a mixture of hydrogen with nitrogen or for example water gas) or of hydro'- gen mixed with carbon dioxide, sulphuretted hydrogen, water vapor or methane or other lydrocarbons. Or the hydrogen may be generate!I in the reaction chamber by the interaction of water and coal, carbon monoxide, hydrocarbons and the like.

It is particularly, advantageous to operate by continuously introducing fresh carbonaceous material intothe reaction vessel and to continuously remove products therefrom. If desired several reaction vessels may be employed in which different conditions of temperature and/or pressure may, if necessary, be maintained and in which different catalysts may also be employed. Suiliciently converted reaction lproducts may be removed after any of the reaction vessels. Materials which have not been suillciently reacted on may be recycled or treated in a further reaction vessel.

The benzines obtained according to the present process when working in the vapor phase are usually characterized by the feature that the fraction thereof boiling between and 190 C. has a particularly low content in hydrogen whereas, as a general rule, it is just this fraction of the benzine which particularly gives rise to knocking when it is employed as a fuel in internal combustion engines. In addition to such benzine a middle oil rich in hydrogen is usually obtained, which may be employed directly as an illuminating oil or as a Diesel oil, or which may be converted into benzine by cracking or a further destructive hydrogenation.

The flow of reaction materials in the process of the present invention is illustrated in the accompanying drawing in which the single figure is a front elevation, partly in section, of an apparatus suitable for carrying out said process. The essential elements of this apparatus and the flow of materials therethru are indicated by appropriatedescriptive legends on said drawing.

'I'he following examples will further illustrate how the invention may be carried out in practice,

but it should be understood that the invention is not restricted to the said examples. 'I'he parts are by weight, unless otherwise stated.

Example 1 From a benzine which has been produced from mineral oil by distillation, a fraction is distilled boiling between and 160 C. and this is passed together with hydrogen at atemperature of 550 C. and under a pressure of 200 atmospheres over af-catalyst prepared from a mixture of vmolybdic acid, zinc oxide and silver iodide, titanium iodide or nickel iodide, the partial pressure of the improved product being maintained at about 30v atmospheres.

A reaction product rich in aromatic hydrocarbons and boiling below C. is obtained. If this product be mixed with a benzine which when used by itself in an internal combustion engine with a high compression `ratio has a tendency to knock, a blended fuel is obtained which is entirely free from these tendencies. f

Example 2 A catalyst is prepared by mixing 70 parts by weight of a tungsten sulphide, prepared by decomposition of ammonium sulphotungstate or by treatment of ammonium tungstate with hydrogen sulphide under a pressure of 5 atmospheres and at a temperature of 410 C. with 30 parts by weight of manganese bromide.- Over this catalyst a middle oil distilled f-rom mineral oil is passed in the vaporous phase together with hydrogen at a temperature of 440 C. and under a pressure of 200 atmospheres. 'I'he product contains 60 per cent of benzine, which has a knock rating corresponding to that of a mixture of about 69 parts of iso-octane and 31 parts of normal pentane. The middle oil is very rich in hydrogen so that it can be employed directly as an illuminating oil.

If manganese bromide is not added to the tungsten sulphide a benzine is obtained which has a knock rating corresponding to a mixture of 63 parts of iso-octane with 37 parts of normal pentane. In place of manganese bromide, titanium bromide, cobalt chloride, chromium bromide, copper iodide or an amount of 5 per cent of tin iodide may be added to the tungsten sulphide.

In place of the above mentioned mixtures pieces of pressed tungsten sulphide may be rigidly arranged in the reaction vessel besides pieces of any of the said halogen compounds.

Example 3 Pit coal is finely ground and mixed with 50 per cent of its weight of a heavy oil obtained by the destructive hydrogenation of the said coal. To this mixture 2 per cent based on the weight of coal of tin iodate is added. This mixture is then spread in the form of a thin layer on plate-like insertions in a high pressure reaction vessel and is heated for 3 hours to a. temperature of about 450 C. in a current of streaming hydrogen under a pressure of 250 atmospheres, 93 per cent of the coal is thus converted into valuable for the most part liquid products which contain less than 5 per cent of asphalt.

In place of the said catalyst cobalt iodide or manganese iodide may be employed.

Example 4 A residue boiling above 325 C. obtained from mineral oils is mixed with 5 per cent of its weight of tin iodide, and is heated in an autoclave for a period of 5 hours to a temperature of 405 C. Prior to the said heating hydrogen is pressed into the autoclave up to an initial pressure of 180 atmospheres. The reaction product on distillation yields 45 per cent of an overhead consisting of benzine and gas oil and 55 per cent of a distillation residue. On subjecting the residue to dewaxing treatment a lubricating oil is obtained having a viscosity of 5.4" Engler at 50 C., a specic gravity of 0.898, a fiat temperature viscosity curve and a green color. By a mere distillation of the residual oil employed as the initial material it is impossible to obtain oil from which by simple dewaxing a lubricating oil can be obtained, since this has too high a content of asphalt.

What we claim is:-

1. A process for the treatment with a hydrogenating gas of a distillable carbonaceous material, which comprises treating the said carbonaceous material with the said gas at a temperature between 250 and '700 C. and under a pressure of at least atmospheres while in contact with a catalyst essentially comprising an iodide of a metal selected from the group consisting of nickel and cobalt and a sulphide of a metal selected from group 6 of the periodic system whereby a substantial amount of liquid product boiling in the gasoline range is produced having good anti-knock properties as a motor fuel.

2. A process according to claim 1 which is carried out in the vapor phase.

3. A process according to claim 1, which is carried out under a pressure of at least 50 atmospheres and at a temperature of between 380 and 550 C.

4. A process according to claim 1 in which the halogen compound consists of nickel iodide and the sulphide ls molybdenum sulphide.

MATHIAS PIER. WALTER SI'MON. WALTER KROENIG. 

